WO2012143149A1

WO2012143149A1 - Method for depositing a transparent barrier layer system

Info

Publication number: WO2012143149A1
Application number: PCT/EP2012/052537
Authority: WO
Inventors: Steffen Günther; Björn MEYER; Steffen Straach; Thomas Kühnel; Sebastian Bunk; Nicolas Schiller
Original assignee: Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V.
Priority date: 2011-04-18
Filing date: 2012-02-15
Publication date: 2012-10-26
Also published as: DE102011017404A1; US20130302536A1; MX2013008814A; JP5930340B2; EP2699705B1; JP2014515787A; EP2699705A1; RU2013136554A; RU2590745C2

Abstract

The invention relates to a method for producing a transparent barrier layer system, wherein in a vacuum chamber at least two transparent barrier layers and a transparent intermediate layer disposed between the two barrier layers are deposited on a transparent plastic film, wherein for deposition of the barrier layers aluminium is vaporised and simultaneously at least one first reactive gas is introduced into the vacuum chamber and wherein for deposition of the intermediate layer aluminium is vaporised and simultaneously at least one second reactive gas and a gaseous or vaporous organic component are introduced into the vacuum chamber.

Description

Method for depositing a transparent barrier layer system

The invention relates to a method for depositing a transparent layer system with a barrier action against water vapor and oxygen.

PRIOR ART Electronically active materials which are used in a wide variety of electronic assemblies often have a high sensitivity to moisture and atmospheric oxygen. In order to protect these materials, it is known to encapsulate such assemblies. This happens on the one hand by the direct deposition of a protective layer on the materials to be protected or by the Elnhausen the modules by means of additional components. For example, solar cells are often made using glass

Protected from moisture and other external influences. In order to save weight and to achieve additional degrees of freedom in terms of design, the

Encapsulate also used plastic sheeting. Such plastic films must be coated for a sufficient protective effect. Therefore, at least one so-called permeation barrier layer (hereinafter also referred to as barrier layer) is deposited on them.

Barrier layers sometimes impose very different resistance on various permeating substances. For the characterization of barrier layers, the permeation of oxygen (OTR) and water vapor (WVTR) by the substrates provided with the barrier layer is frequently used under defined conditions (WVTR according to DIN 531 22-2-A; OTR according to DIN 53380-3).

By coating with a barrier layer, the permeation through a coated substrate over an uncoated substrate is reduced by a factor that is in the single-digit range or can be many orders of magnitude. Frequently, in addition to predefined barrier values, various other target parameters are also expected from a barrier layer. Examples of this are optical, mechanical and technological-economic requirements. For example, barrier layers should often be almost completely transparent in the visible spectral range or beyond. Become Barrier layers used in layer systems, it is often advantageous if

Coating steps for applying individual parts of the layer system can be combined with each other. For the production of barrier layers, so-called PECVD processes (plasma-enhanced chemical vapor deposition) are frequently used. These can be used for coating a wide variety of substrates for different layer materials. For example, it is known to deposit Si0 ₂ and Si ₃ N ₄ layers having a thickness of 20 to 30 nm on 1 μιτι PET substrates [AS da Silva Sobrinho et al., J. Vac. Be. Technol. A 1 6 (6), Nov / Dec 1998, p. 31 90-31 98]. At a working pressure of 10 Pa, permeation values of WVTR = 0.3 g / m ² d and OTR = 0.5 cm ³ / m ² d can be achieved in this way.

When depositing SiO _x for transparent barrier layers on PET substrates by means of PECVD, an oxygen barrier of OTR = 0.7 cm ³ / m ² d can be realized [R. J. Nelson and H. C Hatham, Society of Vacuum Coaters, 34th Annual Technical Conference Proceedings (1991) p. 1 1 3-1 1 7]. In another source, permeation levels of this technology for transparent barrier layers on PET substrates are on the order of magnitude

WVTR = 0.3 g / m ² d and OTR = 0.5 cm ³ / m ² d reported [M. Izu, B. Dotter, SR Ovshinsky, Society of Vacuum Coaters, 36th Annual Technical Conference Proceedings (1993) p. 333- 340].

Disadvantages of the known PECVD methods are, above all, that only relatively small barrier effects are achieved. This makes such barrier layers, in particular for the encapsulation of electronic products uninteresting. Another disadvantage is the high working pressure required to carry out such a process. If such a coating step is to be integrated into complex production processes in vacuum systems, a high outlay for pressure decoupling measures may be required. For this reason, a combination with other coating processes usually becomes uneconomical.

It is also known to apply barrier layers by sputtering. Sputtered monolayers often show better barrier properties than PECVD films. For sputtered AlNO on PET as permeation values, for example WVTR = 0.2 g / m ² d and

OTR = 1 cm ³ / m ² d [Thin Solid Films 388 (2001) 78-86]. In addition, numerous other materials are known, in particular by reactive sputtering for the manufacture of transparent barrier layers are used. However, the layers produced in this way also have too little barrier effects. Another disadvantage of such layers is their low mechanical strength. Damage caused by technologically unavoidable stresses during further processing or use usually leads to a significant deterioration of the barrier effect. This often makes sputtered monolayers unusable for barrier applications. Another disadvantage of sputtered layers is their high cost, which is caused by the low productivity of the sputtering process. It is also known to evaporate individual layers as barrier layers. By means of such PVD methods, various materials can likewise be deposited directly or reactively on a wide variety of substrates. For example, the reactive vapor deposition of PET substrates with Al ₂ O _{3 is} known for barrier applications [Surface and Coatings Technology 1 25 (2000) 354-360]. In this case, permeation values of WVTR = 1 g / m ² d and OTR = 5 cm ³ / m ² d are achieved. This barrier effect is also far too low to be able to use such coated materials as barrier layers for electronic products. They are often mechanically less durable than sputtered single layers. Of advantage, however, are the very high coating rates which are achieved with evaporation processes. These are usually around the factor 1 00 over those which are achieved during sputtering.

It is also known, when depositing barrier layers, to use magnetron plasmas for plasma polymerization (EP 0 81 5 283 B1); [So Fujimaki, H. Kashiwase, Y.

Kokaku, Vacuum 59 (2000) p. 657-664]. These are PECVD processes that are directly maintained by the plasma of a magnetron discharge. An example of this is the use of a magnetron plasma for PECVD coating for

Deposition of layers with a carbon skeleton, with the precursor being CH ₄ . However, such layers also have an insufficient barrier effect for high requirements.

Furthermore, it is known to apply barrier layers or barrier layer systems in several coating steps. One method of this genus is the so-called PML (polymer multilayer) process (1999 Materials Research Society, pp. 247-254); [J. D.

Affinito, ME Gross, CA Coronado, GL Graff, EN Greenweil and PM Martin, Society of Vacuum Coaters, 39th Annual Technical Conference Proceedings (1996) p. 392-397]. In the PML process, a liquid acrylate film is applied to a substrate by means of an evaporator, which is cured by means of electron beam or UV irradiation. This film itself does not have a particularly high barrier effect. Subsequently, a coating of the cured acrylate film with an oxidic intermediate layer, on which in turn an acrylate film is applied. This procedure is repeated several times if necessary. The permeation values of a layer stack produced in this way, ie a combination of individual oxidic barrier layers with acrylic layers as intermediate layers, are below the measurement limit of conventional permeation measuring devices. Disadvantages arise in particular in the necessary use of complex plant technology. In addition, first a liquid film is formed on the substrate, which must be cured. This leads to increased plant contamination, which shortens maintenance cycles. In such coating processes, the intermediate layer functioning as a barrier layer is usually produced by means of magnetron sputtering. Another disadvantage here is that the use of the sputtering technology makes use of a comparatively slow process. This results in very high product costs resulting from the low productivity of the technologies used.

It is known that the mechanical resistance of inorganic vapor deposition layers can be improved if an organic modification is carried out during the evaporation. The incorporation of organic constituents takes place in the inorganic matrix forming during the layer growth. Obviously, the incorporation of these further constituents into the inorganic matrix leads to an increase in the elasticity of the entire layer, which significantly reduces the risk of breaks in the layer. Representative, as at least suitable for barrier applications, in this context, a combination process is called, which combines an electron beam evaporation of SiO _x with the inlet of HMDSO (DE 195 48 1 60 C 1). However, low permeation rates required for electronic components can not be achieved with layers produced in this way. task

The invention is therefore the technical problem of providing a method with which the disadvantages of the prior art are overcome. In particular, the method is intended to provide a transparent barrier layer system with a high blocking effect be produced with respect to oxygen and water vapor and a high coating rate.

The solution of the technical problem results from the articles with the features of claim 1. Further advantageous embodiments of the invention will become apparent from the dependent claims.

In a method according to the invention for producing a transparent barrier layer system, at least two transparent barrier layers are deposited within a vacuum chamber on a transparent plastic film, between which also a transparent intermediate layer is embedded. For depositing the barrier layers, aluminum is vaporized within the vacuum chamber in a reactive process by simultaneously introducing at least one reactive gas, such as oxygen or nitrogen, into the vacuum chamber during the evaporation of the aluminum. The intermediate layer is also deposited by reactively vaporizing aluminum within the vacuum chamber while simultaneously introducing at least one reactive gas, such as oxygen or nitrogen. In addition, during the deposition of the intermediate layer during the evaporation of the aluminum, a gaseous or vaporous organic component is simultaneously introduced into the vacuum chamber. Thus, in forming the intermediate layer, besides the main constituent aluminum, organic constituents are also formed during the process

Layer structure stored. The intermediate layer is thus an aluminum-containing layer with organic constituents or, in other words, an organically modified aluminum-containing layer. For example, precursors and, in particular, silicon-containing precursors such as H MDSO, HMDSN or TEOS are suitable as the organic component which is introduced into the vacuum chamber in gaseous or vapor form.

A transparent barrier layer system deposited by the method according to the invention is distinguished by a high barrier action to water vapor and oxygen and a high load-bearing capacity under flexural and tensile loading, wherein the layer system can also be deposited with the high coating rates known for evaporation. Because of these properties, barrier layer systems deposited according to the invention are suitable, for example, for encapsulating components in solar cell production, OLEDs or electronically active materials. The high barrier effect of the layer system deposited according to the invention with respect to water vapor and oxygen is mainly due to the fact that an organically modified aluminum-containing layer causes a growth stop of layer defects of a barrier layer deposited thereunder by reactive aluminum evaporation. It is known that once formed layer defects, which arise during the reactive evaporation of aluminum, often grow along with the layer growth through the remaining layer thickness. The organically modified aluminum-containing intermediate layer deposited between the barrier layers in the method according to the invention is able to cover the layer defects of the underlying barrier layer so that they do not continue to grow when the second barrier layer overlying the intermediate layer is grown. As a result, it is possible to achieve a high barrier or blocking effect with respect to water vapor and oxygen with a layer system deposited according to the invention. The barrier effect to water vapor and oxygen can be further increased to a certain degree if the barrier layer and intermediate layer are deposited several times in succession alternately.

For evaporation of the aluminum during the deposition of a barrier layer or an intermediate layer known for evaporating Schiffchenverdampfer or electron beam evaporator can be used. The deposition of barrier layer and / or intermediate layer can also be assisted by a plasma which penetrates the space between aluminum evaporator and a plastic film substrate to be coated. This is particularly advantageous when depositing the intermediate layer, because the action of a plasma on a gaseous or vaporous organic component accelerates the splitting of this component and thus promotes the incorporation of organic constituents into the intermediate layer. In particular, hollow cathode plasmas or microwave plasmas are suitable as plasmas.

EXEMPLARY EMBODIMENT The invention will be explained in more detail below with reference to an embodiment. In a 650 mm wide and 75 μιτι thick plastic film made of the material PET, the barrier effect to water vapor should be increased. For this purpose, the plastic film is coated in three test series in a vacuum chamber with different aluminum-containing layers or layer systems. To evaporate the aluminum, eight known boat evaporators are used, which are arranged distributed below the plastic film to be coated with a uniform spacing over the width of the plastic film. The evaporation of the aluminum takes place in all three experiments with an evaporation rate of 2 g / min for each Schiffchen- evaporator, wherein the plastic film is moved away in each case at a belt speed of 50 m / min on the Schiffchenverdampfer. All layers are deposited with plasma support. Four hollow cathodes, which are also distributed with uniform spacing across the width of the plastic film, generate a plasma which penetrates the space between the Schiffchenverdampfern on the one hand and the plastic film to be coated on the other side. The four hollow cathodes are fed with an electrical current of 300 A each.

In a first attempt, only a barrier layer is to be deposited by reactive evaporation of aluminum on the plastic substrate. As the reactive gas, oxygen is used, which flows into the vacuum chamber here and also in the subsequent experiments, each with 1 2 .mu.s slm. For the parameters mentioned, an aluminum oxide layer with a layer thickness of 70 nm is deposited on the plastic film. For this composite of plastic film and aluminum oxide layer, a water vapor barrier effect (WVTR in [g / m 2 / d]) of 0.85 is measured.

In a second experiment, the 70 nm thick barrier layer of aluminum oxide known from the first experiment is first applied to the plastic film. Subsequently, the plastic film provided with the barrier layer is again passed through the vacuum chamber and an organically modified aluminum oxide layer

deposited. Here, the parameters of the aluminum evaporation process are the same as in the deposition of the barrier layer. In addition, during the

Evaporation next to the reactive oxygen gas also the organic component HMDSO with 950 sccm admitted into the vacuum chamber. The effect of the plasma on the HMDSO splits it into components that are in the second

Alumina layer are stored. In this way arises over the

Aluminum oxide barrier layer now an 85 nm thick aluminum oxide layer with organic constituents or in other words an organically modified aluminum oxide layer. For the composite of plastic film,

Alumina layer and organically modified alumina layer, a water vapor barrier effect (WVTR in [g / m 2 / d]) of 0.85 was also measured. The barrier effect has thus not improved compared to the first attempt. However, it was possible to exert a higher strain on the coated plastic film compared with the first test until cracks in the layer system became visible. In the third experiment, according to the invention, a second barrier layer was applied to the organically modified aluminum oxide layer compared to the second experiment, which was deposited with the same parameters as the first barrier layer from the first and second experiments. The result of the third experiment accordingly included a 75 μm PET film, two 70 nm thick barrier layers

Aluminum oxide between which there is an 85 nm thick organically modified aluminum oxide layer. For this composite, a water vapor barrier effect (WVTR in [g / m2 / d]) of 0.45 could be measured. Compared to the first and second tests, the layer system derived from the third experiment had an improved water vapor barrier effect. The load capacity at a strain load was comparable to that from the second attempt. The barrier layer system deposited from the third test according to the method of the invention thus has a high barrier effect to water vapor and also a good load-bearing capacity with respect to a tensile stress. It should be mentioned at this point that the abovementioned values of physical quantities with respect to the reactive aluminum evaporation are given by way of example only and do not restrict the process according to the invention. For the reactive evaporation of the

Aluminum according to the method of the invention can also be applied to any other physical value values known in the art for reactive aluminum evaporation.

Claims

claims

1 . A method for producing a transparent barrier layer system, wherein in a vacuum chamber on a transparent plastic film at least two transparent barrier layers and a disposed between the two barrier layers transparent intermediate layer are deposited, characterized in that for the deposition of the barrier layers aluminum evaporates and at least a first reactive gas into the vacuum chamber is admitted and that evaporated to deposit the intermediate layer of aluminum and at the same time at least a second reactive gas and a gaseous or vaporous organic component are admitted into the vacuum chamber.

2. The method according to claim 1, characterized in that the barrier layer and the second layer are deposited several times alternately.

3. The method according to claim 1 or 2, characterized in that oxygen

and / or nitrogen can be used as the first and / or second reactive gas.

4. The method according to any one of the preceding claims, characterized in that the deposition of the barrier layer and / or the deposition of the second layer in the presence of a plasma in the vacuum chamber.

5. The method according to claim 4, characterized in that a hollow cathode plasma or a microwave plasma is used as plasma.

6. The method according to any one of the preceding claims, characterized in that a silicon-containing precursor is introduced as a gaseous or vaporous organic component in the vacuum chamber.

7. The method according to claim 6, characterized in that HMDSO, H MDSN or TEOS is used as a precursor.